US12194446B2 - SCM-34 molecular sieve, preparation method therefor and use thereof - Google Patents

SCM-34 molecular sieve, preparation method therefor and use thereof Download PDF

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US12194446B2
US12194446B2 US18/245,202 US202118245202A US12194446B2 US 12194446 B2 US12194446 B2 US 12194446B2 US 202118245202 A US202118245202 A US 202118245202A US 12194446 B2 US12194446 B2 US 12194446B2
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molecular sieve
solvent
mixture
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crystallized
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US20230356201A1 (en
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Weimin Yang
Jian Qiao
Zhiqing Yuan
Zhendong Wang
Jiawei Teng
Weichuan TAO
Wenhua FU
Songlin Liu
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority claimed from CN202010962076.8A external-priority patent/CN114180597B/zh
Priority claimed from CN202110438110.6A external-priority patent/CN115231584B/zh
Priority claimed from CN202110699686.8A external-priority patent/CN115504485B/zh
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    • B01J29/82—Phosphates
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
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    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Definitions

  • the present invention pertains to the field of molecular sieve, in particular to a SCM-34 molecular sieve, and preparation method therefor and use thereof.
  • Porous materials are a kind of solid compounds with regular pore structures. According to the definition of the International Union of Pure and Applied Chemistry (IUPAC), porous materials with pore diameters of less than 2 nm are classified as micropore materials; porous materials with pore diameters of more than 2 nm are classified as mesopore materials or macropore materials (with pore diameters of more than 50 nm).
  • Molecular sieve materials generally have pore channel diameters of less than 2 nm, belong to micropore materials and are a kind of porous materials mainly characterized by selective adsorption. Their unique pore channel system renders them capable of sieving small molecules with different sizes, where the name of “molecular sieve” comes.
  • these materials have a wide range of inner pore cavity sizes and have rich and diverse topology structures, have been widely used in fields such as adsorption separation, heterogeneous catalysis, carrier of various guest molecules and ion exchange, and have achieved excellent technical results.
  • zeolite molecular sieves are a kind of crystalline silicate materials, are generally formed by connecting silicon-oxygen tetrahedron [SiO 4 ] 4 ⁇ and aluminum-oxygen tetrahedron [AlO 4 ] 5 ⁇ via shared oxygen atoms, and are generally referred to as TO 4 tetrahedron (a primary structural unit), wherein the silicon element can also be subjected to a partial isomorphous substitution by other elements, in particular some trivalent or tetravalent elements such as Al, B, Ga, Ge, Ti, etc. Owning to some particularities of their structures and chemical properties, zeolite molecular sieves are widely used in catalysis, adsorption, ion exchange and other fields.
  • a key factor deciding the application performance of molecular sieves is the characteristics of their pore channels or cages, which are in turn determined by the intrinsic crystal structure of molecular sieves. Therefore, to obtain a molecular sieve with a new crystal structure is of great significance for exploiting the application of molecular sieves.
  • SAPO-n a non-neutral skeleton composed of SiO 4 , AlO 4 and PO 4 tetrahedrons is formed in the structure of SAPO-n.
  • silicon is present in two ways: (1) replacing one P atom with one Si atom; (2) replacing a pair of aluminum atom and phosphorus atom respectively with two silicon atoms.
  • the representative SAPO-n molecular sieve is an SAPO-34 molecular sieve with a topological structure of CHA.
  • the molecular sieve has a skeleton structure similar to chabasite and belongs to cubic system.
  • the structural motif is composed of AlO 2 ⁇ , SiO 2 and PO 2 + tetrahedrons.
  • the skeleton contains an ellipsoidal supercage and a three-dimensional cross structure with 8-membered ring pore channel.
  • the 8-membered ring pore channel has a pore diameter of about 0.38 nm.
  • the supercage has a pore opening diameter maintained between 0.43 and 0.50 nm.
  • SAPO-34 molecular sieve Due to its suitable proton acidity, larger specific surface area, better adsorption performance, better thermal stability, good hydrothermal stability and excellent shape selectivity of pore channel structure to light olefins, SAPO-34 molecular sieve has been successfully commercialized as the catalyst for methanol to light olefins (MTO), and has shown very good catalytic activity and selectivity.
  • MTO methanol to light olefins
  • molecular sieves with known topological structures are mostly prepared by hydrothermal or solvothermal synthesis.
  • the major steps of a typical hydrothermal or solvothermal synthesis method are: firstly evenly mixing reactants such as the metallic source, the non-metallic source, the organic template and the solvent etc. to obtain an initial sol, i.e., a mixture to be crystallized, and then placing the mixture to be crystallized in a reactor with PTFE as the lining and a stainless steel as the outer wall for a crystallization reaction under a certain temperature and an autogenous pressure after sealing, just like the process of rock formation in the earth, i.e. a process of precipitation of a molecular sieve crystal from a crystallization mixture.
  • the reaction mixture includes skeleton reactants (such as silica sol, phosphoric acid and aluminum oxide), the structure directing agent (SDA) and water, which are uniformly mixed, and is placed in an oven at a fixed temperature (160-220° C.) for several days in a static or dynamic manner for crystallization reaction.
  • skeleton reactants such as silica sol, phosphoric acid and aluminum oxide
  • SDA structure directing agent
  • water which are uniformly mixed, and is placed in an oven at a fixed temperature (160-220° C.) for several days in a static or dynamic manner for crystallization reaction.
  • a solid product containing SAPO-34 molecular sieve is filtered out and dried for the later use.
  • the present invention provides a SCM-34 molecular sieve(, and a preparation method therefor and a use thereof.
  • the SCM-34 molecular sieve is a novel molecular sieve with a new skeleton structure and can be used to prepare a metal-containing AFI type molecular sieve or an SAPO-17 molecular sieve, meeting the different needs for catalysts in the chemical production.
  • a SCM-34 molecular sieve characterized in that the SCM-34 molecular sieve comprises aluminum, phosphorus, oxygen and optionally silicon; in XRD diffraction data of the molecular sieve, a 2 ⁇ degree of the strongest peak within the range of 5-50° is 7.59 ⁇ 0.2; an X-ray diffraction pattern of the SCM-34 molecular sieve includes X-ray diffraction peaks shown in the following table:
  • the present invention further provides a SCM-34 molecular sieve.
  • the SCM-34 molecular sieve has a schematic chemical composition as shown in the formula “Al 2 O 3 : xSiO 2 : yP 2 O”, wherein 0 ⁇ x ⁇ 0.5, 0.75 ⁇ y ⁇ 1.5; in the XRD diffraction data of the molecular sieve, the 2 ⁇ degree of the strongest peak within the range of 5-50° is 7.59 ⁇ 0.2; the X-ray diffraction pattern of the SCM-34 molecular sieve includes X-ray diffraction peaks shown in the following table:
  • the X-ray diffraction pattern of the SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:
  • the X-ray diffraction pattern of the SCM-34 molecular sieve also includes the X-ray diffraction peaks shown in the following table:
  • the incident ray of the X-ray diffraction is CuK ⁇ 1.
  • a method of preparing the aforementioned SCM-34 molecular sieve comprising: crystallizing a mixture containing an aluminum source, a phosphorus source, an organic template R1 and an organic template R2, a solvent S1, a solvent S2 and a solvent S3, and optionally a silicon source to obtain a SCM-34 molecular sieve;
  • the organic template R1 is selected from one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide;
  • the organic template R2 is selected from one or more of imidazole, 2-methylimidazole, 4-methylimidazole, 1-(3-aminopropyl)imidazole, 2-ethyl-4-methylimidazole, pyrrolidine, 1-(3-pyrrolidine)pyrrolidine, N-ethyl-2-aminomethylpyrrolidine;
  • the solvent S1 is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide and N,N-dibutylformamide;
  • the organic template R1 is preferably one or more of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide;
  • the organic template R2 is preferably one or more of 1-(3-aminopropyl) imidazole, 2-ethyl-4-methylimidazole, N-ethyl-2-aminomethylpyrrolidine;
  • the solvent S1 is preferably one or two of N,N-dimethylacetamide and N,N-dibutylformamide;
  • the molar ratio of the organic template R1 to the organic template R2 is 0.01 to 1:1, preferably 0.1 to 0.25:1.
  • the molar ratio of the solvent S1, the solvent S2 and the solvent S3 is 1:0.01-1:1-100, preferably 1:0.05-0.5:10-80.
  • the aluminum source is selected from one or more of aluminum isopropoxide, aluminate, metaaluminate, aluminum salts, hydroxide of aluminum, oxide of aluminum and aluminum-containing minerals, preferably one or two of aluminate and metaaluminate;
  • the silicon source is selected from one or more of organic silicon, amorphous silicon dioxide, silica sol, solid silicon oxide, silica gel, diatomite and water glass, preferably one or more of amorphous silicon dioxide, silica sol and solid silicon oxide;
  • the phosphorus source is selected from at least one of phosphoric acid, ammonium monohydrogen phosphate and ammonium dihydrogen phosphate, preferably orthophosphoric acid.
  • stirring and precipitation treatments are carried out before the crystallization treatment.
  • the stirring time is 0.5-5 hours, the precipitation time is 1-12 hours.
  • the conditions of the crystallization treatment include: the crystallization temperature of 120-200° C., preferably 140-180° C., more preferably 140-160° C.; the crystallization time of 1-5 days, preferably 3-5 days, more preferably 4-5 days.
  • conventional post-processing is carried out, for example the steps of filtering, washing and drying to obtain the molecular sieve; and optionally the step of calcining the obtained molecular sieve.
  • a molecular sieve composition including the SCM-34 molecular sieve described in the aforementioned first aspect or the SCM-34 molecular sieve prepared according to the method described in the aforementioned second aspect, and a binder.
  • a method of preparing the molecular sieve composition comprises the following steps:
  • a use of molecular sieve is provided, that is, the use of the SCM-34 molecular sieve described in the aforementioned first aspect, the SCM-34 molecular sieve prepared according to the method described in the aforementioned second aspect, or the SCM-34 molecular sieve composition described in the aforementioned third aspect for preparing a metal containing AFI type molecular sieve.
  • the metal containing AFI type molecular sieve has a special acid distribution and a novel morphology and is suitable for the methanol-to-olefin reaction.
  • the metal element in the metal containing AFI type molecular sieve is an alkaline earth metal and/or a transition metal element, preferably selected from at least one metal element in the IIA, IIB, IIIB, IVB or VIIIB group, and is further preferably at least one of magnesium, zinc, lanthanum, titanium, cobalt. Based on the mass of the AFI type molecular sieve, the content of the metal element is preferably 0.01%-1.0%.
  • the metal containing AFI molecular sieve has a weak acid center, a medium-strong acid center and a strong acid center at the same time.
  • the acid content distribution is as follows: the weak acid content accounting for 30%-50% of the total acid content, the medium-strong acid content accounting for 5%-20% of the total acid content, and the strong acid content accounting for 30%-65% of the total acid content.
  • a method of preparing the metal containing AFI molecular sieve includes: using the SCM-34 molecular sieve according to the present invention as reactant raw material, mixing it with a solvent SI, an organic template R, a selectively added first silicon source to prepare a precursor A, and then mixing the precursor A with a solvent SII, a metal source, a selectively added second silicon source to prepare the AFI type molecular sieve.
  • the mass ratio of solvent SI to solvent SII is 0.1 to 20:1.
  • preparation method of the AFI type molecular sieve specifically includes the following steps:
  • the organic template R is an organic amine, which is preferably selected from at least one of tetraethylammonium bromide, tetraethylammonium hydroxide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium bromide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltrimethylammonium hydroxide, triethylamine, n-butylamine, di-n-propylamine, diisopropylamine, ethylenediamine and ethylamine, further preferably at least one of tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide and triethylamine.
  • first silicon source or the second silicon source is each independently selected from at least one of organic silicon, amorphous silicon dioxide, silica sol and solid silicon oxide; preferably, at least one of amorphous silicon dioxide, silica sol and solid silicon oxide.
  • step a the heat treatment condition is: 0.5-2 hours at 40-80° C.
  • the crystallization reaction conditions are: 110-160° C., preferably 110-145° C., more preferably 120-135° C.; the reaction time range of 10-120 minutes, preferably 20-100 minutes, more preferably 30-90 minutes.
  • step d the crystallization product can go through post-processing steps, such as filtering, washing, drying, calcining, etc., and conventional operating conditions in the art can be adopted for the post-processing steps.
  • post-processing steps such as filtering, washing, drying, calcining, etc.
  • the obtained product mixture can be subjected to a simple vacuum filtration.
  • the washing for example deionized water and/or ethanol can be used for the washing.
  • the drying temperature for example, 40-250° C., preferably 60-150° C. can be listed, and as the drying time, for example, 3-30 hours, preferably 5-20 hours can be listed.
  • the drying can be carried out under atmospheric pressure or reduced pressure.
  • the calcining can be carried out in any way commonly known in the art, for example, the calcining temperature is generally 300-800° C., preferably 400-650° C., while the calcining time is generally 1-12 hours, preferably 3-12 hours.
  • the calcining is generally carried out in an oxygen containing atmosphere, such as air or oxygen atmosphere.
  • the metal containing AFI type molecular sieve can be used in the reaction of methanol-to-hydrocarbon.
  • the reaction conditions for methanol-to-hydrocarbon are as follows: methanol as raw material, reaction temperature of 400-600° C., reaction pressure of 0.01-10 MPa, and methanol weight space velocity of 0.1-15 h ⁇ 1 .
  • the preparation method of the AFI type molecular sieve according to the present invention allows a rapid crystallization at a lower temperature, for example, the lowest reaction temperature is 110° C., and the fastest reaction time is 10 minutes.
  • the obtained AFI molecular sieve is suitable for the methanol-to-olefin reaction, and has achieved good technical effect.
  • a use of molecular sieve is provided.
  • the SCM-34 molecular sieve described in the aforementioned first aspect, the SCM-34 molecular sieve prepared according to the method described in the aforementioned second aspect, or the SCM-34 molecular sieve composition described in the aforementioned third aspect is used for preparing an SAPO-17 molecular sieve.
  • the SAPO-17 molecular sieve prepared herein has an excellent performance for the use in the industrial production of methanol downstream products, the industrial production of syngas downstream products, and the hydrocarbon cracking.
  • the preparation method of SAPO-17 molecular sieve includes the following steps:
  • the first organic solvent cS and the second organic solvent cS are each independently selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-epoxycyclopentane, 1,4-dioxane, cyclohexanone, cyclohexanol; preferably, at least one of 1,4-dioxane, cyclohexanone.
  • the mass ratio of the added SCM-34 molecular sieve, the organic template cR and all the organic solvents cS is 0.1-1: 1-10:1-10, wherein, all the organic solvents are the total amount of the first organic solvent cS in step 1) and the second organic solvent cS in step 2).
  • the mass ratio of the first organic solvent cS in step 1) to the second organic solvent cS in step 2) is 1:0.1-1.
  • the temperature of the first heat treatment is 40-90° C., the time is 1-5 hours; preferably, the temperature of the first heat treatment is 55-75° C., the time is 2-4 hours.
  • the temperature of the second heat treatment is 40-90° C., the time is 1-5 hours; preferably, the temperature of the second heat treatment is 50-70° C., the time is 2-3 hours.
  • the mass ratio of the silicon source to the SCM-34 molecular sieve is 0 to 10:1, preferably 0.1 to 10:1.
  • the silicon source is at least one of organic silicon, amorphous silicon dioxide, silica sol, silica, silica gel, diatomite and water glass; preferably, at least one of amorphous silica, silica sol and silica.
  • the mixing is preferably adding the precursor P into the mixture material M while stirring, the stirring time is 0.5 to 5 hours, preferably 2.5 to 4 hours.
  • the pretreatment condition is stirring for 0.5 to 5 h at 80 to 110° C.
  • step 4 the conditions of the crystallization reaction are: crystallization for 1 to 8 hours at 115 to 140° C.
  • the SAPO-17 molecular sieve can be used in the reactions of methanol-to-hydrocarbon and syngas-to-olefin.
  • reaction conditions for the methanol-to-hydrocarbon are as follows: methanol as raw material, reaction temperature of 400-600° C., reaction pressure of 0.01-10 MPa, methanol weight space velocity of 0.1-15 h ⁇ 1 .
  • the SAPO-17 molecular sieve prepared according to the present invention is used to the reaction of methanol-to-hydrocarbon, within the set evaluation conditions, the methanol conversion rate is 100%, the single pass yields of ethylene and propylene are up to 84.5%, and the selectivity ratio (ethylene/propylene) is in the range of 2.5-3.0, the catalyst has good stability.
  • the highest CO conversion rate is up to 51.7%
  • the highest C 2 -C 4 olefin selectivity is up to 85.6%
  • the selectivity ratio (ethylene/propylene) is in the range of 2.5-3.0.
  • the preparation of the SAPO-17 molecular sieve according to the method of the present invention involves a shorter crystallization time, can shorten the total synthesis time of SAPO-17 molecular sieve to a certain extent at the same time, and can be conducted at a lower temperature.
  • the SAPO-17 molecular sieve prepared by the crystal transformation of the SCM-34 molecular sieve according to the present invention significantly improves the use performance of SAPO-17 molecular sieve.
  • the SAPO-17 molecular sieve synthesized by this method shows an excellent performance during the use in the industrial production of methanol downstream products, the industrial production of syngas downstream products, and the cracking of hydrocarbons.
  • the total yields of ethylene and propylene are high, and the selectivity ratio (ethylene/propylene) is high.
  • the selectivity of C 2 -C 4 olefins is high, the selectivity ratio (ethylene/propylene) is high.
  • FIG. 1 is the X-ray diffraction (XRD) pattern of the molecular sieve prepared in Example 1;
  • FIG. 2 is the SEM photo of the molecular sieve prepared in Example 1;
  • FIG. 3 is the XRD pattern of the AFI type molecular sieve synthesized in Example 9;
  • FIG. 4 and FIG. 5 are the SEM photos of the AFI type molecular sieve synthesized in Example 9;
  • FIG. 6 shows the TPD pattern of the AFI type molecular sieve synthesized in Example 9
  • FIG. 7 is the XRD pattern of the SAPO-17 molecular sieve in Example 13;
  • FIG. 8 is the SEM photo of the SAPO-17 molecular sieve in Example 13;
  • FIG. 9 is the XRD pattern of the SAPO-17 molecular sieve in Comparative Example 1;
  • FIG. 10 shows the SEM photos of SAPO-17 molecular sieve in Comparative Example 1.
  • XRD X-ray diffraction pattern
  • an X'Pert PRO X-ray powder diffractometer (XRD) manufactured by PANalytical B.V. is used, with a working voltage of 40 kV, a current of mA and a scanning range of 3.5-50°.
  • the product morphology is photographed with S-4800 Field Emission Scanning Electron Microscope (Fe-SEM) manufactured by HITACHI of Japan.
  • the X-ray diffraction pattern data are shown in Table 1, the X-ray diffraction pattern is shown in FIG. 1 , and the SEM is shown in FIG. 2 .
  • Al(iPr) 3 aluminum isopropoxide
  • phosphoric acid purity ⁇ 85 wt.
  • 294.8 g of tetrabutylammonium hydroxide 40 wt. % aqueous solution, MkSeal
  • 569.1 g of 1-(3-aminopropyl) imidazole were then added to the solution C to obtain a solution C′ after stirring for 5 hours, precipitating for 1 hour.
  • 15.0 g of acidic silica sol Lidox HS type, 40 wt.
  • the above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 90° C. for 10 hours to obtain a product SCM-34.
  • the X-ray diffraction pattern data are shown in Table 3, and the XRD pattern is similar to FIG. 1 .
  • the above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 100° C. for 8 hours to obtain a product SCM-34.
  • the X-ray diffraction pattern data are shown in Table 5, and the XRD pattern is similar to FIG. 1 .
  • the above mixture to be crystallized was placed at 140° C. for crystallization for 5 days. After filtering, washing, the product was dried at 100° C. for 8 hours to obtain a product SCM-34.
  • the X-ray diffraction pattern data are shown in Table 6, and the XRD pattern is similar to FIG. 1 .
  • the precursor A was fed to the mixture B under a closed stirring condition, the stirring was continued for 3.5 hours and was further continued for 1 hour at 85° C. Then it was crystallized at 160° C. for 10 min, dried at 100° C. for 6 hours after filtering and washing, then heated to 600° C., calcined at a constant temperature for 4 hours, and thus an AFI molecular sieve (the same below) was obtained, marked as SSP5-1.
  • SSP5-1 contains 0.18 wt. % Mg element. Its XRD pattern is similar to FIG. 3 , SEM pattern is similar to FIG. 4 and FIG. 5 , and the metal content and the acid distribution in the product are listed in Table 7.
  • the precursor A was fed into the mixture B under a closed stirring condition, the stirring was continued for 0.5 hours and was further continued for 0.5 hours at 100° C. under a closed state.
  • the above mixture after stirring was then crystallized at 110° C. for 120 min, filtered, washed, and then dried at 90° C. for 8 hours, then heated to 500° C., calcined at a constant temperature for 8 hours to obtain a product, marked as SSP5-2.
  • the SSP5-2 contains 0.01 wt. % Co element. Its XRD pattern is similar to FIG. 3 , SEM pattern is similar to FIG. 4 and FIG. 5 , and the metal content and the acid distribution in the product are listed in Table 7.
  • the SSP5-3 contains 1.0 wt. % Zn element. Its XRD pattern is FIG. 3 , SEM pattern is FIG. 4 and FIG. 5 , TPD pattern is FIG. 6 , and the metal content and the acid distribution in the product are listed in Table 7.
  • the SSP5-1 molecular sieve synthesized in Example 7 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 505° C., a mass space velocity of 3.5 h ⁇ 1 and a pressure of 1.7 MPa. The yields of ethylene, propylene and butylene were up to 96.8%. Good technical results were obtained.
  • the SSP5-2 molecular sieve synthesized in Example 8 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use.
  • methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 400° C., a mass space velocity of 0.5 h ⁇ 1 and a pressure of 5.1 MPa.
  • the yields of ethylene, propylene and butylene were up to 92.6% and good technical results were obtained.
  • the SSP5-3 molecular sieve synthesized in Example 9 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and screened. 12-20 meshes of particles were selected for later use. Using methanol as raw material and a fixed bed reactor with a diameter of 15 mm, an assessment was carried out under the conditions of 600° C., a mass space velocity of 0.1 h ⁇ 1 and a pressure of 0.01 MPa. The yields of ethylene, propylene and butylene were up to 90.9% and good technical results were obtained.
  • HCHA cyclohexylamine
  • PIP piperazine
  • DOA 1,4-dioxane
  • CHO cyclohexanone
  • the precursor P 3 was fed into the mixture material M 3 under the condition of vigorous stirring. The stirring was continued for 1 hour, a closed stirring was then carried out at 100° C. for 1 hour, and crystallization was then carried out at 120° C. for 5 hours. After filtering, washing, the product was dried at 80° C. for 9 hours, then heated to 400° C., and calcined at a constant temperature for 8 hours, and a product was obtained, marked as STE-3. Its XRD pattern is similar to FIG. 7 , and its SEM pattern is similar to FIG. 8 .
  • SAPO-17 molecular sieve was prepared according to the synthesis method of SAPO-17 molecular sieve disclosed in CN103922361A, which is specifically as follows: with aluminum isopropoxide as aluminum source, phosphoric acid as phosphorus source, silica sol as silicon source, and cyclohexylamine as template, 81 g of aluminum isopropoxide was added to 48.9 g of ultrapure water, and 45.7 g of phosphoric acid (85 wt. %) was added after stirring evenly. After stirring for 1 hour, 11.5 mL of cyclohexylamine was added to the mixed solution, and after 2 hours of stirring and aging, 11.9 g of 30 wt.
  • % SiO 2 aqueous solution was added to the system. After several hours of continuous aging, the sol was placed in a stainless steel reactor with a PTFE lining and crystallized at 200° C. for 120 hours to obtain a short and thick rod-like SAPO-17 molecular sieve. See FIG. 9 for its XRD pattern and FIG. 10 for its SEM pattern.
  • the synthesis method of SAPO-17 molecular sieve is specifically: with aluminum isopropoxide as aluminum source, phosphoric acid as phosphorus source, silica sol as silicon source, and cyclohexylamine as template, according to a solution of a reaction ratio of 1Al 2 O 3 :1P 2 O 5 :0.3SiO 2 :1CHA:1HF:40H 2 O and a fixed amount of aluminum source of 0.015 mol, 3.06 g of aluminum isopropoxide was added to 5.4 g of deionized water, 1.7 g of phosphoric acid (85 wt.
  • the STE-1 molecular sieve synthesized in Example 13 was calcined at 550° C. for 4 hours, cooled to room temperature, then tableted, smashed and sieved, and 12-20 meshes of particles were selected for later use.
  • methanol as raw material and a fixed bed reactor with a diameter of 15 mm
  • an assessment was conducted under the conditions of 600° C., a mass space velocity of 4.9 h ⁇ 1 , and a pressure of 1.0 MPa.
  • the methanol conversion rate was 100%, the yields of ethylene, propylene in the product were up to 78.7%, and the selectivity ratio (ethylene/propylene) was 2.87. Good technical results were obtained.
  • the STE-2 molecular sieve synthesized in Example 14 was used to prepare a catalyst according to the catalyst preparation method in Example 16.
  • methanol as raw material and a fixed bed reactor with a diameter of 15 mm
  • an assessment was carried out under the conditions of 550° C., a mass space velocity of 15 h ⁇ 1 , and a pressure of 10 MPa.
  • the methanol conversion rate was 100%
  • the yields of ethylene, propylene in the product were up to 80.8%
  • the selectivity ratio (ethylene/propylene) was 2.76. Good technical results have been achieved.
  • the STE-3 molecular sieve synthesized in Example 15 was used to prepare a catalyst according to the catalyst preparation method in Example 16.
  • methanol as raw material and a fixed bed reactor with a diameter of 15 mm
  • an assessment was carried out under the conditions of 474° C., a mass space velocity of 7.1 h ⁇ 1 , and a pressure of 2.4 MPa.
  • the methanol conversion rate was 100%
  • the yields of ethylene, propylene in the product were up to 84.5%
  • the selectivity ratio (ethylene/propylene) was 2.99. Good technical results have been achieved.
  • the SAPO-17 molecular sieve synthesized in Comparative Example 1 was used to prepare a catalyst according to the catalyst preparation method of Example 16.
  • the methanol conversion rate was 100%
  • the yields of ethylene, propylene in the product were up to 33.3%
  • the selectivity ratio (ethylene/propylene) was 1.1.
  • the SAPO-17 molecular sieve synthesized in Comparative Example 2 was used to prepare a catalyst according to the catalyst preparation method of Example 16.
  • the methanol conversion rate was 100%
  • the yields of ethylene, propylene in the product were up to 40.1%
  • the selectivity ratio (ethylene/propylene) was 1.2.
  • the STE-1 molecular sieve synthesized in Example 13 was calcined at 550° C. for 6 hours, then tableted, smashed, screened, and 20-40 meshes of particles were selected.
  • a weight ratio of catalyst to filler ZnCrO x /STE 1.0 (ZnCrO x represents a mixture of zinc oxide and chromium oxide, and an oxide-molecular sieve catalyst was prepared for later use) was used.
  • the STE-2 molecular sieve synthesized in Example 14 was used to prepare a catalyst according to the catalyst preparation method in Example 19.
  • the STE-3 molecular sieve synthesized in Example 15 was used to prepare a catalyst according to the catalyst preparation method in Example 19.
  • the SAPO-17 molecular sieve synthesized in Comparative Example 2 was used to prepare a catalyst according to the catalyst preparation method of Example 20.
  • the CO conversion rate was 22.3%, wherein the C 2 -C 4 olefin selectivity was 36.8%, and the selectivity ratio (ethylene/propylene) was 1.21.

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